The present invention relates to a process for producing a catalyst for xcex1-olefin polymerization, and a process for producing an xcex1-olefin polymer. In more detail, the present invention relates to (1) a process for producing a highly stereoregular xcex1-olefin polymer, which has (i) a high bulk density. (ii) an extremely low content of a catalyst residue and an amorphous polymer, and (iii) an excellent mechanical property and processability, and (2) a process for producing a catalyst for xcex1-olefin polymerization, which can produce said polymer.
There are known (1) a process for producing a catalyst for xcex1-olefin polymerization, which comprises the steps of:
(i) reducing a titanium compound containing a tetravalent titanium with an organomagnesium compound in the presence of an organosilicon compound to obtain an eutectic crystal compound of magnesium and titanium (Tixe2x80x94Mg complex solid catalyst component), and
(ii) contacting the eutectic crystal compound with an organoaluminum compound and an organosilicon compound (electron donor compound): and (2) a process for producing an xcex1-olefin polymer using said catalyst (for example, JP 3-43283-B and JP 1-319508-A).
There is proposed a reduction step, wherein the above-mentioned reduction step is carried out in the presence of an ester compound in addition to the organosilicon compound.
However, each of the above-mentioned processes has a problem that the higher activity an obtained catalyst has, the lower bulk density an obtained xcex1-olefin polymer has.
As a process for producing an olefin polymer having a high bulk density, there are proposed (1) a polymerization process of ethylene using a solid catalyst component, wherein a titanlum-magnesium compound is supported on a silica gel, and (2) a polymerization process of propylene using a solid catalyst component, wherein a silica gel is impregnated with a titanium-magnesium compound.
However, those processes have problems that (1) an obtained catalyst has a low polymerization activity, and (2) an obtained polymer contains such a large quantity of silica gel that an obtained product is not preferable in view of quality and appearance.
An object of the present invention is to provide (1) a process for producing a highly stereoregular xcex1-olefin polymer, which has (1) a high bulk density, (ii) an extremely low content of a catalyst residue and an amorphous polymer, and (iii) an excellent mechanical property and processability, and (2) a process for producing a catalyst for xcex1-olefin polymerization, which can produce said polymer.
The present invention provides a process for producing a catalyst for xcex1-olefin polymerization, which comprises the steps of:
(1) reducing a titanium compound represented by the following formula (1) with an organomagnesium compound in the presence of an organosllicon compound having an Sixe2x80x94O bond to produce a reduction solid (hereinafter, this step is referred to as xe2x80x9cstep (1)xe2x80x9d),
(2) aging the reduction solid for at least 18 hours in an inert solvent under stirring intermittently to produce a solid product (hereinafter, this step is referred to as xe2x80x9cstep (2)xe2x80x9d),
(3) contacting the solid product with an ether compound, titanium tetrachloride and an organic acid halide compound, and then heating a resultant mixture to produce an organic acid halide-treated solid (hereinafter, this step is referred to as xe2x80x9cstep (3)xe2x80x9d),
(4) contacting the organic acid halide-treated solid with a mixture of an ether compound, titanium tetrachloride and an ester compound, or with a mixture of an ether compound and titanium tetrachloride, and then heating a resultant mixture to produce a solid catalyst component containing a titanium compound (hereinafter, this step is referred to as xe2x80x9cstep (4)xe2x80x9d), and
(5) contacting the solid catalyst component with an aluminum compound and an electron donor compound to produce a catalyst for xcex1-olefin polymerization (hereinafter, this step is referred to as xe2x80x9cstep (5)xe2x80x9d):
Ti (OR1)aX4-axe2x80x83xe2x80x83(1)
wherein R1 is a hydrocarbon group having 1 to 20 carbon atoms; X is a halogen atom; and a is a number satisfying 0 less than axe2x89xa64.
The present invention also provides a process for producing an xcex1-olefin polymer, which comprises the step of homopolymerizing an xcex1-olefin, or copolymerizing at least one kind of an xcex1-olefin and ethylene in the presence of a catalyst for xcex1-olefin polymerization produced by the above-mentioned process.
Examples of R1 in the formula (1) are alkyl groups such asmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, decyl and dodecyl groups; aryl groups such as phenyl, cresyl, xylyl and naphthyl groups; allyl groups such as a propenyl group; and aralkyl groups such as a benzyl group. Among them, alkyl groups having 2 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms are preferable, and straight-chain alkyl groups having 2 to 18 carbon atoms are particularly preferable. As the compound represented by the above formula (1), it is allowed to use those having two or more OR1 groups different from one another.
As X in the formula (1), a chlorine atom, a bromine atom and an iodine atom are exemplified. Of these, a chlorine atom is particularly preferred.
A preferable a in the formula (1) is a number satisfying 2xe2x89xa6axe2x89xa64, and a particularly preferable a is 4.
The compound represented by the formula (1) can be produced by a process known in the art, such as (1) a process comprising the step of reacting Ti(OR1)4 with TiX4 in a predetermined ratio, and (2) a process comprising the step of reacting Tix4 with a corresponding alcohol (for example, R1OH) in a predetermined ratio.
Examples of the compound represented by the formula (1) are titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; hydrocarbyloxytitanium trihalides such as methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride and ethoxytitanium tribromlde; dihydrocarbyloxytitanium dihalides such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride and diethoxytitanium dibromide; trihydrocarbyloxytitanium monohalides such as trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride and triethoxytitanium bromide; and tetrahydrocarbyloxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium and tetraphenoxytitanium.
Examples of the organosilicon compound used in the present invention are compounds represented by the following formulas (2) to (4):
Si(OR2)mR34-mxe2x80x83xe2x80x83(2)
R4(R52SiO)pSiR63xe2x80x83xe2x80x83(3)
(R72SiO)qxe2x80x83xe2x80x83(4)
wherein R2 is a hydrocarbon group having 1 to 20 carbon atoms; R3, R4, R5, R6 and R7 are independently of one another a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom; m is a number satisfying 0 less than mxe2x89xa64; p is an integer of from 1 to 1000; and q is an integer of from 2 to 1000.
Examples of the organosilicon compound are tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-isopropoxysilane, di-isopropoxy-di-isopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydlbutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldilsiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethyl polysiloxane, diphenyl polysiloxane, methylhydro polyslloxane and phenylhydro polysiloxane. Among these, preferable are compounds represented by the formula (2), and among them, compounds wherein m is a number satisfying 1xe2x89xa6mxe2x89xa64are preferable, and tetraalkoxysilane compounds wherein m=4 are particularly preferable.
Examples of the ester compounds used in the present invention are mono-carboxylic acid esters and poly-carboxylic acid esters. Examples of said compounds are aliphatic carboxylic acid esters, alicyclic carboxylic acid esters and aromatic carboxylic acid esters.
Examples of the ester compounds are methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate. ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl sucCinate, diethylmalonate, dibutylmalonate, dimethylmaleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-octyl phthalate and diphenyl phthalate. Among them, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters and phthalic acid esters are preferable, and diesters of phthalic acid are particularly preferalbe.
The xe2x80x9corganomagnesium compoundxe2x80x9d used in the present invention means any types of organomagnesium compounds having a Mg-carbon bond. As said compound, preferable is (i) a Grignard compound represented by the following formula (5), or (ii) a dialkylmagnesium compound or a diarylmagnesium compound represented by the following formula (6):
R8MgXxe2x80x83xe2x80x83(5)
R9R10Mgxe2x80x83xe2x80x83(6)
wherein R8 is a hydrocarbon group having 1 to 20 carbon atoms; X is a halogen atom; and R9 and R10 are independently of each other a hydrocarbon group, having 1 to 20 carbon atoms, which may be the same or different from each other.
Examples of R8, R9 and R10 in the above formulas are alkyl, aryl, aralkyl and alkenyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, isoamyl, hexyl, octyl, 2-ethylhexyl, phenyl and benzyl groups.
Examples of compounds represented by the formula (5) are methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, propylmagnesium chloride, propylmagnesium bromide, butylmagriesiumchloride, butylmagnesium bromide, sec-butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, amylmagnesium chloride, isoamylmagnesium chloride hexylmagnesium chloride, phenylmagnesium chloride and phenylmagnesium bromide.
Examples of compounds represented by the formula (6) are dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, di-sec-butylmagnesium, di-tert-butylmagnesium, butyl-sec-butylmagnesium, diamylmagnesium, dlhexylmagnesium, diphenylmagnesium and butylethylmagnesium.
Examples of solvents for producing the organomagnesium compound are an ether solvent such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, dilsoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, phenetol, anisole, tetrahydrofuran and tetrahydropyrane; a hydrocarbon solvent such as hexane, octane, cyclohexane, methylcyclohexane, benzene, toluene and xylene; and a mixed solvent comprising two or more thereof.
It is preferable to use an ether solution of the organomagnesium compound. Examples of the ether are an ether having at least six carbon atoms in its molecule, and an ether having a cyclic structure. Among them, an ether solution of the compound represented by the formula (5) is palrticularly preferable from a viewpoint of performances of a polymerization catalyst obtained. It is permitted to use the organomagnesium compound in combination with an orgenometallic compound to form a hydrocarbon soluble complex. Examples of the organometallic compounds are compounds of Li, Be, B. Al and Zn.
Examples of an ether compound used in the present invention are dialky ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctylether, methyl butyl ether, methyl isoamyl ether and ethyl Jsobutyl ether. Among them, diisobutyl ether or diisoalmyl ether is particularly preferable.
Examples of an organic acid halide used in the present invention are mono-carboxylic acid halides and poly-carboxylic acid halides. Specific examples of those compounds are aliphatic carboxylic acid halides, alicyclic carboxylic acid halides and aromatic carboxylic acid halides.
Examples of the organic acid halide compound are acetyl chloride, propionic chloride, butyric chloride, valeric chloride, acrylic chloride, methacrylic chloride, benzoic chloride, toluic chloride, anisic chloride, succinic chloride, malonic chloride, maleic chloride, itaconic chloride and phthalic chloride. Of these, aromatic carboxylic acid chlorides such as benzoic chloride, toluic chloride and phthalic chloride are preferable, and phthalic chloride is particularly preferable.
All of the steps (1) to (5) are carried out in an atmosphere of an inert gas such as argon.
Examples of a method for carrying out the reduction reaction in the step (1) are (i) a method of adding the organomagnesium compound into a mixture containing the organosilicon compound and the titanium compound, and (ii) a method of adding a mixture containing the organosilicon compound and the titanium compound into a solution containing the organomagnesium compound. Among them, the method (1) is preferable from aviewpoint of performances of a polymerization catalyst obtained.
It is preferable to use the titanium compound and the organosilicon compound dissolved in or diluted with a suitable solvent. Examples of the solvent are aliphatic hydrocarbons such as hexane, heptane, octane and decane; aromatic hydrocarbons such as toluene andxylene: alicyclichydrocarbons such as cyclohexane, methylcyclohexane and decalin; and ether compounds such as diethyl ether, dibutyl ether, diusoamyl ether and tetrahydrofuran.
A temperature in the reduction reaction is usually from xe2x88x9250 to 70xc2x0 C., preferably from xe2x88x9230 to 50xc2x0 C., and particularly preferably from xe2x88x9225 to 35xc2x0 C. When the temperature is too high, an activity of an obtained polymerization catalyst is low.
It is possible to impregnate a porous material with the solid product by carrying out the reduction reaction in the presence of the porous material such as an inorganic oxide and an organic polymer. Preferable porous materials are those, whIch have (1) a volume of micro pores having a radius of from 20 to 200 nm of 0.3 ml/g or more, and (2) an average particle diameter of from 5 to 300 xcexcm.
Examples of the inorganic porous material are SiO2, Al2O3, MgO, TiO2, ZrO2, SiO2. Al2O3 complex oxide, MgO. Al2O3 complex oxide and MgO. Sio2. Al2O3 complex oxide. Examples of the organic porous material are a polystyrene-based polymer, a polyacrylate-based polymer, a polyacrylonitrile-based polymer, a polyvinyl chloride-based polymer and apolyolefin-based polymer. Specific examples thereof are polystyrene, a styrene-divinylbenzene copolymer, a styrene-n,nxe2x80x2-alkylenedlmethacrylamide copolymer, a styrene-ethylene glycol-methyl dimethacrylate copolymer, polyethylacrylate, armethyl acrylate-divinylbenzene copolymer, an ethyl acrylate-divinylbenzene copolymer, polymethylmethacrylate, a methyl methacrylate-divinylbenzene copolymer, a polyethylene glycol-methyl dimethacrylate copolymer, polyacrylonitrile, an acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinyl pyrrolidine, polyvinyl pyridine, an ethylvinyl benzene-divinylbenzene copolymer, polyethylene, an ethylene-methyl acrylate copolymer and polypropylene. Among them, preferable is SiO2, Al2O3 or a styrene-divinylbenzene copolymer.
A total adding time required in the above-mentioned methods (i) and (ii) regarding the reduction reaction in the step (1) is not limited, and is usually from about 30 minutes to about 12 hours. In order to complete the reduction reaction, an additional reaction may be carried out at 0 to 120xc2x0 C. after said adding.
The organosilicon compound is used in an amount of usually from 1 to 50, preferably from 3 to 30, and particularly preferably from 5 to 25 in terms of an atomic ratio Si/Ti, i.e. a ratio of a silicon atom in the organosilicon compound to a titanium atom in the titanium compound.
The organomagnesium compound is used in an amount of usually from 0.1 to 10, preferably from 0.2 to 5.0, and particularly preferably from 0.5 to 2.0 in terms of an atomic ratio (Ti+Si)/Mg, i.e. a ratio of the sum of a titanium atom in the titanium compound and a silicon atom in the organosilicon compound to a magnesium atom in the organomagnesium compound.
The reduction solid obtained by solid-liquid separation of the reaction mixture obtained in the step (1) is usually washed several times with an inert solvent such as hexane, heptane and toluene. Said reduction solid contains a trivalent titanium atom, magnesium and a hydrocarbyloxy group, and generally has an amorphous structure or extremely low crystallinity. A reduction solidhaving an amorphous structure is preferable from a viewpoint of performances of a catalyst obtained.
The solid product is produced by carrying out the step (2) using said reduction solid. Examples of an Inert solvent used in said step are inert hydrocarbon solvents such as hexane, heptane and toluene. An aging temperature is usually from xe2x88x9250 to 70xc2x0 C., preferably from xe2x88x9230 to 50xc2x0 C., and particularly preferably from xe2x88x9225 to 35xc2x0 C. An aging time is usually 18 hours or more, and preferably 30 hours or more.
As a contacting order in the step (3), there is exemplified an order of contacting the solid product with a mixture of the ether compound and titanium tetrachloride, and then contacting with the organic acid halide compound. By contacting with the organic acid halide compound, there can be produced a polymerization catalyst, which can accomplish an object of the present invention.
The ether compound in the step (3) is used in an amount of usually from 0.1 to 100 mol, preferably from 0.5 to 50 mol, and particularly preferably from 1 to 20 mol per one mol of a titanium atom contained in the solid product.
Titanium tetrachloride in the step (3) is added in an amount of usually from 1 to 1000 mol, preferably from 3 to 500 mol, and. particularly preferably from 10 to 300 mol per one mol of a titanium atom contained in the solid product; and usually from 1 to 100 mol, preferably from 1.5 to 75 mol, and particularly preferably from 2 to 50 mol per one mol of the ether compound.
The organic acid halide compound is used in an amount of usually from 0.1 to 50 mol, more preferably from 0.3 to 20 mol, and particularly preferably from 0.5 to 10 mol per one mol of a titanium atom contained in the solid product; and usually from 0.01 to 1.0 mol, and preferably from 0.03 to 0.5 mol per one mol of a magnesium atom contained in the solid product. When said amount exceeds 50 mol in the former, or exceeds 1.0 mol in the latter, destruction of the solid product may occur.
A contacting method in the step (3) is not limited. As said method, there can be exemplified methods known in the art such as a slurry method and a mechanically pulverizing method using a ball mill. Among them, a slurry method, wherein contacting is carried out in the presence of a diluent, is preferable.
Examples of said diluent are aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene. Among them, particularly preferable is an aromatic hydrocarbon or a halogenated hydrocarbon. The diluent is used in an amount of usually from 0.1 to 1000 ml, and preferably from 1 to 100 ml per one g of the solid product.
An example of an embodiment of the step (3) is an embodiment comprising the steps of (1) adding the diluent and a mixture of the ether compound and titanium tetrachloride to the solid product at 85xc2x0 C. or lower, and preferably 75xc2x0 C. or lower, to obtain a solid product slurry, (ii) heating the solid product slurry at usually from xe2x88x9250 to 150xc2x0 C., and preferably from 0 to 120xc2x0 C., for usually 30 minutes or longer, and preferably from 1 to 10 hours, and (iii) solid-liquid separating after allowing to stand, and washing the obtained solid several times with an inert hydrocarbon solvent to obtain the organic acid halide-treated solid.
The step (4) is preferably carried out in a slurry state. Examples of a solvent for the slurry are aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; and halogenated hydrocarbons such as dichloroethene, trichloroethene, monochlorobenzene, dichlorobenzene and trichlorobenzene. Among them, preferable is a halogenated hydrocarbon or an aromatic hydrocarbon.
A concentration of said slurry is generally form 0.05 to 0.7 g-solid/ml-solvent, and particularly preferably from 0.1 to 0.5 g-solid/ml-solvent. A contacting temperature in the step (4) is generally form 30 to 150xc2x0 C., preferably from 45 to 135xc2x0 C., and particularly preferably from 60 to 120xc2x0 C. A contacting time is not particularly limited, and generally preferably form 30 minutes to 6 hours.
Examples of a contacting method in the step (4) are (i) a method wherein the ether compound, titanium tetrachloride and optionally the ester compound are added to the organic acid halide-treated solid obtained in the step (3), and (ii) a method wherein the organic acid halide-treated solid is added to a solution containing the ether compound, titanium tetrachloride and optionally the ester compound. Among the method (i), preferable is (a) a method wherein the ether compound and optionally the ester compound are added to the organic acid halide-treated solid, and then titanium tetrachloride is added, or (b) a method wherein the ether compound, titanium tetrachloride and optionally the ester compound are added simultaneously to the organic acid halide-treated solid. Particularly preferable is a method wherein a mixture containing the ether compound, titanium tetrachloride and optionally the ester compound is added to the organic acid halide-treated solid.
A contacting number of times in the step (4) is one time or more. Preferable is two times or more from a viewpoint of an activity of a polymerization catalyst obtained and stereoregularity of a polymer obtained.
The ether compound in the step (4) is used in an amount of usually from 0.1 to 100 mol, preferably from 0.5 to 50 mol, and particularly preferably from 1 to 20 mol per one mol of a titanium atom contained in the solid product obtained in the step (2). Titanium tetrachloride is added in an amount of usually from 1 to 1000 mol, preferably from 3 to 500 mol, and particularly preferably from 10 to 300 mol per one mol of a titanium atom contained in the solid product obtained in the step (2);: and in an amount of usually from 1 to 100 mol, preferably from 1.5 to 75 mol, and particularly preferably from 2 to 50 mol per one mol of the ether compound.
When using the ester compound in the step (4), the ester compound is used in an amount of not more than 30 mol, preferably not more than 15 mol, and particularly preferably not more than 5 mol per one mol of a titanium atom contained in the solid product obtained in the step (2).
The steps (3) and (4) are preferably carried out in a closed reaction vessel. Pressure in the reaction vessel rises gradually from an ambient pressure to about 300 KpaG with a lapse of a contacting time due to generation of vapor of materials added to the reaction vessel, an organic solvent and gaseous reaction by-products. However, it is preferable not to purge any gas out of the reaction vessel.
The solid catalyst component used In the step (5) is generally obtained by washing a solid several times, which solid is obtained by solid-liquid separating the reaction mixture obtained in the step (4), with an inert hydrocarbon solvent such as hexane and heptane. Preferably, said solid is washed at from 50 to 120xc2x0 C. at least one time with lots of a halogenated hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent such as toluene, and is further washed several times with an aliphatic hydrocarbon solvent such au hexane, from a viewpoint of an activity of a polymerization catalyst obtained and stereoregularity of a polymer obtained.
The organoaluminum compound used in the step (5) means a compound having at least one Al-carbon bond in the molecule. Typical examples thereof are those represented by the following formulas (7) and (8):
R11rAlY3-rxe2x80x83xe2x80x83(7)
R12R13Alxe2x80x94Oxe2x80x94AlR14R15xe2x80x83xe2x80x83(8)
wherein R11 to R12 are independently of one another a hydrocarbon group having 1 to 20 carbon atoms; Y is a halogen atom, a hydrogen atom or an alkoxy group; and r is a number satisfying 2xe2x89xa6rxe2x89xa63.
Examples of said organoaluminum compound are trialkylaluminums such as triethylaluminum, tri-isobutylaluminum and trihexylaluminum; dialkylaluminum hydrides suchas diethylaluminumhydrideanddi-isobutylaluminum hydride; dialkylaluminum halides such as diethylaluminum chloride; mixtures of trialkylaluminums and dialkylaluminum halides such as a mixture of triethylaluminum and diethylaluminum chloride; and alkylalumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane. Among these, trialkylaluminums, mixtures of trialkylaluminums and dialkylaluminum halides, or alkylalumoxanes are preferable, and triethylaluminum, tri-isobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialumoxane are particularly preferable.
The organoaluminun compound is used in an amount of usually from 0.5 to 1000 mol, and particularly preferably from 1 to 600 mol per one mol of the titanium atom contained in the solid catalyst component.
Examples of the electron donor compound used in the step (5) are oxygen-containing electron donor compounds such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid esters, inorganic acid esters, ethers, acid amides and acid anhydrides; and nitrogen-containing electron donor compounds such as ammonia, amines, nitrites and isocyanates. Of these, inorganic acid esters or ethers are preferable.
As the above-mentioned inorganic acid esters, preferable are silicon compounds represented by the following formula (9):
R16nSi(OR17)4-nxe2x80x83xe2x80x83(9)
wherein R16 is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom; R17 is a hydrocarbon atoms having 1 to 20 carbon atoms; each of R16 and R17 may have different substituent (s) in the same molecule; and n is a number satisfying 0xe2x89xa6n less than 4.
Examples of said silicon compounds are tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrirethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxyailane, isopropyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldi-methoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, tert-butylmethyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, hexylmethyldnmethoxysilane, hexylethyldimethoxysilane, dodecymethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyalopentylisobutyldimithoxysilane, cyclopentyi-tert-butyldlmethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldirmethoxysilane, cyclohaxylisobutyldlmethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, dlphenyldimethoxysilane, phenylmethyld:lmethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, vinylmethyldlmethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, tert-butyltriethoxysllane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, dilsobutyldiethoxysilane, di-tert-butyldiethoxysilane, butylmethyldiethoxysilane, butylethyldiethoxysilane, tert-butylmethyldiethoxysiane, hexylmethyldiethoxysilane, hexylethyldiethoxysilane, dodecylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, phenyl-tri-tert-butoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, trimethylphenoxysilane and methyltriallyloxysilane.
Preferable examples of the above-mentioned ethers are a dialkylether and a diether compound represented by the following formula (10): 
wherein R18 to R21 are independently of one another a straight-or branched-chain alkyl group, an alicyclic group, an aryl group or an aralky group having 1 to 20 carbon atoms, and R18 or R19 may be independently of each other a hydrogen atom.
Examples of the ethers are diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, ethyl isobutyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-dilsopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane and 2-heptyl-2-pentyl-1,3-dimethoxypropane.
As the electron donor compound, particularly preferable is an organosilicon compound represented by the following formula (10):
R22R23Si (OR24)2xe2x80x83xe2x80x83(10).
In the formula (10). R22 is a C3-20 hydrocarbon group, wherein a carbon atom adjacent to Si is secondary or tertiary. Examples of R27 are branched-chain alkyl groups such as an isopropyl group, a sec-butyl group, a tert-butyl group and a tert-amyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group: cycloalkenyl groups such as a cyclopentenyl group; and aryl groups such as a phenyl group and a tolyl group.
In the formula (10), R23 is a C1-20 hydrocarbon group. Examples of R23 are straight-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group; branched-chain alkyl groups such as an isopropyl group, a sec-butyl group, a tert-butyl group and a tert-amyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; cycloalkenyl groups such as a cyclopentenyl group; and aryl groups such as a phenyl group and a tolyl group.
In the formula (10), R24 is a C1-20, and preferably C1-5 hydrocarbon group.
Examples of said organosilicon compound are diisopropyldimethoxysilane, diisobutyldinethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tart-butyl-n-ptropyldimethoxysilane, tert-butyl-n-butyldirmethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tsrt-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldinethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane. cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysllane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphanyldimethoxysilane, diphenyldrmethoxysllane, phenymethyldimethoxysilane, phenylisopropyldimethoxygilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldinethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cycohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane and 2-norbornanemethyldiethoxysilane.
The xcex1-olefin used in the present invention is that having not less than 3 carbon atoms, and preferably from 3 to 10 carbon atoms. Examples of the xcex1-olefin are straight chain monolefins such as propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and decene-1; branched chain monolefins such as 3-methylbutene-1, 3-methylpentene-1 and 4-methylpenetene-1; vinylcyclohexane; and a combination of two or more thereof. Of these, preferableishomopolymerizationof propyleneorbutene-1, or copolymerization of a mixture of olefins containing propylene or butene-1 as a main component; and particularly preferable is homopolymerization of propylene, or copolymerization of amixture of olefins containing propylene as a main component.
In the copolymerization, it is permitted to copolymerize at least two kinds of xcex1-olefins with ethylene. Further, it is permitted to copolymerize a compound having several unsaturated bonds such as a conjugated diene and a non-conjugated diene. A copolymerization method may be a hetero-block copolymerization method, wherein polymerization is carried out in two or more stages.
Tn the step (5) and in the process for producing an xcex1-olefin polymer in accordance with the present invention, amethod for supplying catalyst components such as the solid catalyst component, the organoaluminum compound and the electron donor compound into apolymerizationvessel is not particularlylimited. Preferable is a method, wherein supplying is carried out in an inert gas such as nitrogen and argon under water free conditions. Specific examples of the method are (1) a method wherein the above-mentioned components are separately supplied to a polymerization vessel, and (2) amethod wherein any two components of the above-mentioned components are pre-mixed, and then the resultant pre-mixture and the remaining component are supplied to a polymerization vessel.
In the process for producing an xcex1-olefin polymer in accordance with the present invention, the above-mentioned catalyst itself may be used (such a polymerization is hereinafter referred to as xe2x80x9creal polymerizationxe2x80x9d), or a pre-polymerized catalyst obtained by pre-polymerizing said polymerization catalyst as follows may be used.
The pre-polymerized catalyst can be generally produced by polymerizing (pre-polymerizing) a few amount of an olefin in the presence of the solid catalyst component and the organoaluminum compound. A preferable pre-polymerlzation method is a slurry polymerization method, wherein an inert hydrocarbon such as propane, butane, isobutane pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene is used as a solvent. It is allowed to use an olefin in place of a part or total of said solvent.
In the pre-polymerization, the organoaluminum compound is used in an amount of usually from 0.5 to 700 mol, preferably from 0.8 to 500 mol, and particularly preferably from 1 to 200 mol per one mol of the titanium atom contained in the solid catalyst component.
An amount of the olefin pre-polymerized is usually from 0.01 to 1000 g, preferably from 0.05 to 500 g, and particularly preferably from 0.1 to 200 g per one g of the solid catalyst component.
A concentration of the slurry in the above-mentioned slurry polymerization is preferably from 1 to 500 g-solid catalyst component/liter-solvent, and particularly preferably from 3 to 300 g-solid catalyst component/llter-solvent. A pre-polymerization temperature is preferably from xe2x88x9220 to 100xc2x0 C., and particularly preferably from 0 to 80xc2x0 C. A partial pressure of the olefin in the gas phase portion in the pre-polymerization is preferably from 0.01 to 20 kg/cm2, and particularly preferably from 0.1 to 10 kg/cm2, but the olefin which is liquid at the pre-polymerization pressure and temperature is not limited thereto. A pre-polymerization time is not particularly limited, and it is usually preferably from 2 minutes to 15 hours.
In the pre-polymerization, examples of a method for supplying the solid catalyst component, the organoaluminum compound and the olefin are (1) amethodwherein the solid catalyst component and the organoaluminum compound are supplied, and thereafter the olefin is supplied, and (2) a method wherein the solid catalyst component and the olefin are supplied, and thereafter the organoaluminum compound is supplied. Examples of a method for supplying the olefin are (1) a method wherein the olefin Is supplied one after another, while keeping a pressure in a polymerization vessel at a predetermined level, and (2) a method wherein the total amount of the olefin predetermined is supplied at a time. It is permitted to use a chain transfer agent such as hydrogen in order to regulate a molecular weight of an olefin polymer obtained in the pre-polymerization.
In the pre-polymerization, if necessary, a part or the total amount of the above-mentioned electron donor compound may be used. In the pre-polymerization, the electron donor compound is used in an amount of usually from 0.01 to 400 mol, preferably from 0.02 to 200 mol, and particularly preferably from 0.03 to 100 mol per one mol of the titanium atom contained in the solid catalyst component; and usually from 0.003 to 5 mol, preferably from 0.005 to 3 mol, and particularly preferably from 0.01 to 2 mol per one mol of the organoaluminum compound.
In the pre-polymerization, a method for supplying the electron donor compound to a polymerization vessel is not particularly limited. Examples of the method are (1) a method wherein only said compound is supplied, and (2) a method wherein a contact product of said compound with the organoaluminum compound is supplied. The olefin used in the pre-polymerization may be the same as or different from that used in the real polymerization.
Examples of amethod for real-polymerizing are (1) amethod wherein the olefin is polymerized in the presence of a catalyst obtained by contacting the solid catalyst component, the organoaluminum compound and the electron donor compound, (2) a method wherein the olefin is polymerized in the presence of the pre-polymerized catalyst, and (3) a method wherein the olefin is polymerized in the presence of a contact product obtained by contacting said pre-polymerized catalyst, the organoaluminum compound and the electron donor compound.
In the real polymerization, the organoaluminum compound is used in an amount of usually from 1 to 1000 mol, and particularly preferably from 5 to 600 mol per one mol of the titanium atom contained in the solid catalyst component.
In the real polymerization, the electron donor compound is used in an amount of usually from 0.1 to 2000 mol, preferably from 0.3 to 1000 mol, and particularly preferably from 0.5 to 800 mol per one mol of the titanium atom contained in the solid catalyst component; and usually from 0.001 to 5 mol, preferably from 0.005 to 3 mol, and particularly preferably from 0.01 to 1 mole per one mol of the organoaluminum compound.
A temperature of the real polymerization is usually from xe2x88x9230 to 300xc2x0 C., and preferably from 20 to 180xc2x0 C. A polymerization pressure is not particularly limited, and from an industrial and economical point of view, it is usually from atmospheric pressure to 100 kg/cm2, and preferably from about 2 to 50 kg/cm2. The polymerization may be carried out in either a batch-wise manner or a continuous manner. Examples of a polymerization method are a slurry or solution polymerization method, wherein an inert hydrocarbon solvent such as propane, butane, lsobutane, pentane, hexane, heptane and octane is used; a bulk polymerization method, wherein an olefin which is liquid at the polymerization temperature is used as a medium; and a gas phase polymerization method.
In the real polymerization,iit is permitted to use a chain transfer agent such as hydrogen in order to regulate a molecular weight of an olefin polymer obtained.